Gilman reagents ketones

The addition of a lithium dialkylcuprate (Gilman reagent) to an acyl chloride at low temperatures produces a ketone. This method produces a good yield of acetophenone. 

Fig. 13.30. 1,4-Addition plus enolate altylation—a one-pot process for the a- and -functionalization of a,/3-unsatu-rated ketones. Two quaternary C atoms can be constructed via addition of a Gilman reagent and subsequent alkylation with Mel.

Acid chlorides react just once with dialkylcuprates (Gilman reagents) to give ketones (Section 18-10). 

R2CuLi /C=C lithium dialkyl cuprate (Gilman reagents) enamine O II H2C=CH —C —H O II H2C=CH—C—R conjugated aldehyde conjugated ketone... 

The reaction of Gilman reagents with ,)8 -epoxy-oximes yields -hydroxy-ketones [e.g. (17 X=OH)].56 Vinyl copper compounds are converted stereo-specifically into /3,/3-disubstituted a-ethylenic acids by carbonation nerol (18) was synthesized (Scheme 3).57 Further papers on /3-ketosulphoxide synthesis [e.g. of... 

Alkanes, RH (Sec. 7.7) (Sec. 10.7) (Sec. 10.8) (Sec. 19.9) from alkenes by catalytic hydrogenation from alkyl halides by protonolysis of Grignard reagents from alkyl halides by coupling with Gilman reagents from ketones and aldehydes by Wolff-Kishner reaction... 

The ketone intermediate formed during the Grignard reaction of an acid chloride can t usually be isolated because addition of the second equivalent of organomagnesium reagent occurs too rapidly. A ketone can, how-, ever, be isolated from the reaction of an acid chloride with a diorganoi p per (Gilman) reagent (Section 19.2) ... 

To stop at the ketone stage, a weaker organometallic reagent is needed one that reacts faster with acid chlorides than with ketones. A lithium dialkylcuprate (Gilman reagent) is such a reagent. 

Acid chlorides react readily with lithium diorganocopper (Gilman) reagents (Section 15.2) to give ketones, as illustrated by the conversion of pentanoyl chloride to 2-hexanone. The reaction is carried out at -78°C in either diethyl ether or tetrahy-drofuran. Following hydrolysis in aqueous acid, the ketone is isolated in good yield. 

Acid chlorides react with Gilman reagents to give ketones. 

What combination of an a,P-unsaturated ketone and a Gilman reagent is required to synthesize each of the following compounds ... 

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